(2,2′-Bipyridine-κ²N,N′)dibromido(dimethyl sulfoxide-κO)zinc(II)

In the mol­ecule of the title compound, [ZnBr₂(C₁₀H₈N₂)(C₂H₆OS)], the Zn^II atom is five-coordinated in a distorted trigonal–bipyramidal configuration by two N atoms from one 2,2′-bipyridine, one O atom from one dimethyl­sulfoxide molecule and two Br atoms. Inter­molecular π–π stacking between parallel pyridine rings [face-to-face distance 3.32 (4) Å] and C—H...Br and C—H...O hydrogen-bonding interactions are present in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.058
• wR factor = 0.140
• Data-to-parameter ratio = 24.3

checkCIF/PLATON results

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Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          7
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         35

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   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
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   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
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S1. Comment

There are several Zn^II complexes containing 2,2'-bipyridine and 2,2'-bipyridine derivatives such as, [ZnCl₂(bipy)], (II), (Khan & Tuck, 1984), [ZnCl₂(5,5'-dmbpy)], (III), (Khalighi et al., 2008), [ZnCl₂(6-mbpy)], (IV), (Ahmadi, et al., 2008), [ZnCl₂(6,6'-dmbpy)], (V), (Alizadeh, Kalateh, Ebadi, et al., 2009), [ZnBr₂(6,6'-dmbpy)], (VI), (Alizadeh, Khoshtarkib et al., 2009), [ZnI₂(6,6'-dmbpy)], (VII), (Alizadeh, Kalateh, Khoshtarkib et al., 2009), [ZnCl₂(bipy)(DMSO)], (VIII), (Marjani et al., 2007) and [ZnBr₂(4,4'-(dtbpy)].(Et₂O), (IX), (Blake et al., 2007) [where bipy is 2,2'-bipyridine, 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dmbpy is 6,6'-dimethyl-2,2'-bipyridine, DMSO is dimethyl sulfoxide and dtbpy is 4,4'-di-tert-butyl-2,2'-bipyridine] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound (I).

In the molecule of the title compound, (I), (Fig. 1), the Zn^II atom is five-coordinate in a distorted trigonal-bipyramidal configurations by two N atoms from one 2,2'-bipyridine, one atom from one dimethyl sulfoxide and two Br atoms. The Zn—N and Zn—O bond lengths and angles (Table 1) are within normal range (VIII) and Zn—Br bond lengths and angles are within normal range (VI).

The π-π contacts between the pyridine rings, Cg1···Cg3ⁱ, Cg2···Cg2ⁱⁱ, Cg2···Cg3ⁱ, Cg3···Cg1ⁱ and Cg3···Cg2ⁱ [symmetry cods: (i) 1-X,1-Y,1-Z, (ii) 1-X,-Y,1-Z, where Cg1, Cg2 and Cg3 are centroids of the rings (Zn1/N1/C5—C6/N2), (N1/C1—C5) and (N2/C6—C10), respectively] with centroid-centroid distance of 3.475 (3), 3.661 (3), 3.721 (3), 3.476 (3) and 3.721 (3) Å, respectively, and intramolecular C—H···O and C—H···Br hydrogen bonding it seems effective in the stabilization of the crystal structure (Fig. 2).

Related literature

For related structures, see: Ahmadi et al. (2008); Alizadeh, Kalateh, Ebadi et al. (2009); Alizadeh, Kalateh, Khoshtarkib et al. (2009); Alizadeh, Khoshtarkib et al. (2009); Blake et al. (2007); Khan & Tuck (1984); Marjani et al. (2007); Khalighi et al. (2008).

S2. Experimental

For the preparation of the title compound, (I), a solution of 2,2'-bipyridine (0.17 g, 1.10 mmol) in methanol (10 ml) was added to a solution of ZnBr₂ (0.25 g, 1.10 mmol) in methanol (5 ml) at room temperature. The suitable crystals for X-ray diffraction experiment were obtained by methanol diffusion to a colorless solution in DMSO. Suitable crystals were isolated after one week (yield; 0.36 g, 71.2%).

S3. Refinement

H atoms were positioned geometrically with C—H = 0.93 Å for aromatic and 0.96 Å for methyl, and constrained to ride on their parent atoms with U_iso(H)=1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Unit-cell packing diagram for (I).

(2,2'-Bipyridine-κ²N,N')dibromido(dimethyl sulfoxide-κO)zinc(II)

Crystal data

[ZnBr2(C10H8N2)(C2H6OS)]	F(000) = 896
Mr = 459.51	Dx = 1.938 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 653 reflections
a = 9.4802 (10) Å	θ = 2.1–29.2°
b = 8.3449 (7) Å	µ = 6.76 mm^−1
c = 19.989 (2) Å	T = 298 K
β = 95.185 (8)°	Block, colorless
V = 1574.9 (3) Å^3	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	4245 independent reflections
Radiation source: fine-focus sealed tube	3229 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
φ and ω scans	θmax = 29.2°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
Tmin = 0.148, Tmax = 0.260	k = −11→11
12674 measured reflections	l = −27→25

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0602P)^2 + 1.8278P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max = 0.005
4245 reflections	Δρmax = 1.08 e Å^−3
175 parameters	Δρmin = −1.46 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0087 (7)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5556 (5)	0.1151 (7)	0.3831 (3)	0.0377 (10)
H1	0.5286	0.0980	0.3378	0.045*
C2	0.6783 (5)	0.0424 (7)	0.4117 (3)	0.0425 (12)
H2	0.7333	−0.0208	0.3859	0.051*
C3	0.7166 (6)	0.0660 (7)	0.4788 (3)	0.0462 (13)
H3	0.7982	0.0185	0.4992	0.055*
C4	0.6335 (5)	0.1603 (6)	0.5155 (3)	0.0383 (10)
H4	0.6581	0.1772	0.5611	0.046*
C5	0.5129 (5)	0.2297 (6)	0.4840 (2)	0.0295 (9)
C6	0.4154 (5)	0.3323 (6)	0.5190 (2)	0.0311 (9)
C7	0.4311 (6)	0.3600 (7)	0.5883 (2)	0.0406 (11)
H7	0.5056	0.3137	0.6150	0.049*
C8	0.3346 (6)	0.4570 (7)	0.6166 (3)	0.0432 (12)
H8	0.3433	0.4771	0.6625	0.052*
C9	0.2254 (5)	0.5234 (7)	0.5759 (3)	0.0422 (12)
H9	0.1589	0.5889	0.5939	0.051*
C10	0.2162 (5)	0.4915 (7)	0.5085 (3)	0.0395 (11)
H10	0.1421	0.5366	0.4812	0.047*
C11	0.2234 (7)	0.7783 (10)	0.2635 (4)	0.0621 (18)
H11A	0.3167	0.7412	0.2564	0.075*
H11B	0.2302	0.8683	0.2935	0.075*
H11C	0.1750	0.8099	0.2213	0.075*
C12	−0.0109 (6)	0.7414 (10)	0.3256 (4)	0.0650 (19)
H12A	0.0281	0.8281	0.3529	0.078*
H12B	−0.0698	0.6765	0.3514	0.078*
H12C	−0.0665	0.7838	0.2872	0.078*
N1	0.4750 (4)	0.2084 (5)	0.41813 (19)	0.0324 (8)
N2	0.3090 (4)	0.3984 (5)	0.48005 (19)	0.0324 (8)
O1	0.2163 (4)	0.5774 (5)	0.36384 (18)	0.0440 (9)
Zn1	0.29167 (5)	0.33824 (7)	0.37552 (3)	0.03244 (16)
Br1	0.37506 (6)	0.34269 (8)	0.26199 (3)	0.04918 (19)
Br2	0.07887 (6)	0.17861 (8)	0.37356 (3)	0.05171 (19)
S1	0.12833 (14)	0.62307 (17)	0.29876 (7)	0.0413 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.040 (2)	0.040 (3)	0.033 (2)	0.006 (2)	0.0043 (19)	−0.001 (2)
C2	0.042 (3)	0.038 (3)	0.049 (3)	0.009 (2)	0.012 (2)	−0.001 (2)
C3	0.041 (3)	0.044 (3)	0.052 (3)	0.009 (2)	−0.002 (2)	0.008 (3)
C4	0.038 (2)	0.041 (3)	0.035 (2)	−0.001 (2)	−0.0051 (18)	0.004 (2)
C5	0.032 (2)	0.028 (2)	0.028 (2)	−0.0061 (17)	0.0007 (16)	0.0022 (17)
C6	0.0297 (19)	0.031 (2)	0.032 (2)	−0.0062 (17)	0.0025 (16)	−0.0013 (19)
C7	0.043 (3)	0.047 (3)	0.031 (2)	−0.006 (2)	−0.0026 (19)	−0.001 (2)
C8	0.052 (3)	0.049 (3)	0.029 (2)	−0.008 (2)	0.008 (2)	−0.003 (2)
C9	0.046 (3)	0.040 (3)	0.043 (3)	0.000 (2)	0.018 (2)	−0.001 (2)
C10	0.037 (2)	0.043 (3)	0.039 (2)	0.005 (2)	0.0079 (19)	0.004 (2)
C11	0.047 (3)	0.080 (5)	0.060 (4)	−0.005 (3)	0.010 (3)	0.026 (4)
C12	0.040 (3)	0.071 (5)	0.086 (5)	0.006 (3)	0.014 (3)	0.022 (4)
N1	0.0333 (18)	0.034 (2)	0.0299 (18)	0.0003 (15)	0.0015 (14)	0.0026 (16)
N2	0.0278 (17)	0.039 (2)	0.0309 (18)	−0.0022 (15)	0.0029 (14)	−0.0005 (17)
O1	0.053 (2)	0.041 (2)	0.0352 (18)	0.0093 (16)	−0.0089 (15)	0.0020 (16)
Zn1	0.0303 (3)	0.0378 (3)	0.0285 (3)	0.0010 (2)	−0.00125 (19)	0.0005 (2)
Br1	0.0467 (3)	0.0704 (4)	0.0309 (2)	0.0102 (3)	0.0059 (2)	0.0055 (3)
Br2	0.0373 (3)	0.0562 (4)	0.0604 (4)	−0.0122 (2)	−0.0025 (2)	−0.0009 (3)
S1	0.0409 (6)	0.0409 (7)	0.0397 (6)	0.0015 (5)	−0.0084 (5)	0.0036 (5)

Geometric parameters (Å, º)

C1—N1	1.333 (6)	C9—H9	0.9300
C1—C2	1.388 (7)	C10—N2	1.338 (6)
C1—H1	0.9300	C10—H10	0.9300
C2—C3	1.372 (8)	C11—S1	1.761 (7)
C2—H2	0.9300	C11—H11A	0.9600
C3—C4	1.372 (8)	C11—H11B	0.9600
C3—H3	0.9300	C11—H11C	0.9600
C4—C5	1.382 (6)	C12—S1	1.770 (7)
C4—H4	0.9300	C12—H12A	0.9600
C5—N1	1.345 (6)	C12—H12B	0.9600
C5—C6	1.480 (6)	C12—H12C	0.9600
C6—N2	1.336 (6)	Zn1—N1	2.157 (4)
C6—C7	1.401 (6)	Zn1—N2	2.141 (4)
C7—C8	1.380 (8)	S1—O1	1.529 (4)
C7—H7	0.9300	Zn1—O1	2.125 (4)
C8—C9	1.374 (8)	Zn1—Br1	2.4701 (8)
C8—H8	0.9300	Zn1—Br2	2.4148 (8)
C9—C10	1.369 (7)
N1—C1—C2	122.6 (5)	S1—C11—H11B	109.5
N1—C1—H1	118.7	H11A—C11—H11B	109.5
C2—C1—H1	118.7	S1—C11—H11C	109.5
C3—C2—C1	118.5 (5)	H11A—C11—H11C	109.5
C3—C2—H2	120.7	H11B—C11—H11C	109.5
C1—C2—H2	120.7	S1—C12—H12A	109.5
C2—C3—C4	119.4 (5)	S1—C12—H12B	109.5
C2—C3—H3	120.3	H12A—C12—H12B	109.5
C4—C3—H3	120.3	S1—C12—H12C	109.5
C3—C4—C5	119.2 (5)	H12A—C12—H12C	109.5
C3—C4—H4	120.4	H12B—C12—H12C	109.5
C5—C4—H4	120.4	C1—N1—C5	118.4 (4)
N1—C5—C4	121.8 (5)	C1—N1—Zn1	124.5 (3)
N1—C5—C6	114.5 (4)	C5—N1—Zn1	117.1 (3)
C4—C5—C6	123.6 (4)	C6—N2—C10	118.9 (4)
N2—C6—C7	121.0 (4)	C6—N2—Zn1	117.3 (3)
N2—C6—C5	115.8 (4)	C10—N2—Zn1	123.7 (3)
C7—C6—C5	123.2 (4)	S1—O1—Zn1	118.7 (2)
C8—C7—C6	119.1 (5)	O1—Zn1—N2	83.24 (15)
C8—C7—H7	120.4	O1—Zn1—N1	139.98 (15)
C6—C7—H7	120.4	N2—Zn1—N1	75.19 (15)
C9—C8—C7	119.1 (5)	O1—Zn1—Br2	104.13 (11)
C9—C8—H8	120.4	N2—Zn1—Br2	97.80 (11)
C7—C8—H8	120.4	N1—Zn1—Br2	111.81 (11)
C10—C9—C8	118.8 (5)	O1—Zn1—Br1	90.99 (11)
C10—C9—H9	120.6	N2—Zn1—Br1	152.93 (11)
C8—C9—H9	120.6	N1—Zn1—Br1	93.27 (11)
N2—C10—C9	123.1 (5)	Br2—Zn1—Br1	109.25 (3)
N2—C10—H10	118.5	O1—S1—C11	105.3 (3)
C9—C10—H10	118.5	O1—S1—C12	104.2 (3)
S1—C11—H11A	109.5	C11—S1—C12	97.7 (4)
N1—C1—C2—C3	1.0 (9)	C9—C10—N2—C6	0.4 (8)
C1—C2—C3—C4	−0.2 (9)	C9—C10—N2—Zn1	177.1 (4)
C2—C3—C4—C5	−0.1 (8)	S1—O1—Zn1—N2	−159.5 (3)
C3—C4—C5—N1	−0.5 (8)	S1—O1—Zn1—N1	143.3 (2)
C3—C4—C5—C6	179.5 (5)	S1—O1—Zn1—Br2	−63.2 (3)
N1—C5—C6—N2	−4.3 (6)	S1—O1—Zn1—Br1	47.0 (3)
C4—C5—C6—N2	175.7 (4)	C6—N2—Zn1—O1	−146.3 (4)
N1—C5—C6—C7	175.5 (4)	C10—N2—Zn1—O1	36.9 (4)
C4—C5—C6—C7	−4.5 (7)	C6—N2—Zn1—N1	−0.3 (3)
N2—C6—C7—C8	0.1 (8)	C10—N2—Zn1—N1	−177.1 (4)
C5—C6—C7—C8	−179.7 (5)	C6—N2—Zn1—Br2	110.3 (3)
C6—C7—C8—C9	0.2 (8)	C10—N2—Zn1—Br2	−66.5 (4)
C7—C8—C9—C10	−0.2 (8)	C6—N2—Zn1—Br1	−67.5 (5)
C8—C9—C10—N2	−0.1 (8)	C10—N2—Zn1—Br1	115.7 (4)
C2—C1—N1—C5	−1.5 (8)	C1—N1—Zn1—O1	−119.4 (4)
C2—C1—N1—Zn1	175.5 (4)	C5—N1—Zn1—O1	57.6 (4)
C4—C5—N1—C1	1.2 (7)	C1—N1—Zn1—N2	−179.1 (4)
C6—C5—N1—C1	−178.8 (4)	C5—N1—Zn1—N2	−2.2 (3)
C4—C5—N1—Zn1	−175.9 (4)	C1—N1—Zn1—Br2	88.3 (4)
C6—C5—N1—Zn1	4.0 (5)	C5—N1—Zn1—Br2	−94.7 (3)
C7—C6—N2—C10	−0.4 (7)	C1—N1—Zn1—Br1	−24.0 (4)
C5—C6—N2—C10	179.4 (4)	C5—N1—Zn1—Br1	153.0 (3)
C7—C6—N2—Zn1	−177.3 (4)	Zn1—O1—S1—C11	−120.4 (4)
C5—C6—N2—Zn1	2.5 (5)	Zn1—O1—S1—C12	137.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br1	0.93	2.86	3.413 (6)	119
C10—H10···O1	0.93	2.53	2.979 (7)	110